CN100339405C - Liquid absorbing sheet and non-aqueous electrolyte battery pack - Google Patents
Liquid absorbing sheet and non-aqueous electrolyte battery pack Download PDFInfo
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- CN100339405C CN100339405C CNB2004800045581A CN200480004558A CN100339405C CN 100339405 C CN100339405 C CN 100339405C CN B2004800045581 A CNB2004800045581 A CN B2004800045581A CN 200480004558 A CN200480004558 A CN 200480004558A CN 100339405 C CN100339405 C CN 100339405C
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Abstract
A liquid absorbing sheet comprising a liquid absorbing resin layer having excellent liquid absorption properties to a nonaqueous electrolytic solution of a constituent nonaqueous electrolyte secondary battery of a nonaqueous electrolyte battery pack (particularly, a lithium-ion nonaqueous electrolyte secondary battery pack) is disclosed. The liquid absorbing resin layer is formed by applying, to a supporting base, a monomer composition containing a monofunctional monomer component (A) containing a monofunctional monomer (a) which can form a homopolymer that is soluble to the nonaqueous solvent of the nonaqueous electrolyte secondary battery and a multifunctional monomer component (B), and irradiating the thus-obtained coating film with ultraviolet light, thereby causing polymerization.
Description
Technical field
When the present invention relates to, be used to the non-aqueous electrolyte battery pack that absorbs the liquid-absorbent sheet of this electrolytic solution and use this liquid-absorbent sheet by the nonaqueous electrolytic solution unit generation electrolytic solution leakage in the non-aqueous electrolyte battery pack.
Background technology
The cell box that has held a plurality of primary celies unit or secondary battery cell and wired circuit board in battery case is extensive use of for people always.In this cell box, during by the leakage of battery unit generation electrolytic solution, can corrode in the wiring of wired circuit board, have that conduction takes place is bad or cause the possibility of short circuit conversely.Therefore, even under the situation that the electrolytic solution leakage takes place, also can not produce above-mentioned corrosion or problem of short-circuit, proposed in cell box with contacted position of battery unit or contiguous position on configuration have the liquid-absorbent member of liquid-absorbant, wherein liquid-absorbant has the ability (spy opens the 2001-351588 communique) of Electolyte-absorptive.Here, as liquid-absorbant, use the various macromolecular materials of adsorptive type, gelation type, self expending type.Particularly, can enumerate polyacrylate absorbent resin, starch-graft copolymer class absorbent resin, polyvinyl alcohol absorbent resin, polyacrylamide absorbent resin, iso-butylene-maleic acid absorbent resin, the acrylate cross linked polymkeric substance of chain alkyl, polynorbornene etc.
But, these liquid-absorbants, for utilizing more and more widely, constitute non-aqueous electrolyte battery pack in recent years, especially constituting the widely used carbonates solvent of nonaqueous electrolytic solution secondary battery of lithium ion nonaqueous electrolytic solution secondary battery box, for example propylene carbonate or methylcarbonate, existence can not fully absorb the problem of liquid.
The present invention attempts to solve the problem that exists in the above conventional art, the cell box that purpose is to provide the nonaqueous electrolytic solution for the nonaqueous electrolytic solution secondary battery that constitutes non-aqueous electrolyte battery pack (particularly lithium ion nonaqueous electrolytic solution secondary battery box) to demonstrate the absorbefacient liquid-absorbent sheet of excellent liquid and possess the electrolytic solution absorption component that is formed by this liquid-absorbent sheet.
Summary of the invention
The inventor finds, by monomer composition irradiation ultraviolet radiation to the polymerizable ultraviolet type that contains the monofunctional monomer composition (A) that comprises the monofunctional monomer (a) that can form the homopolymer of the non-aqueous solvent that is dissolved in nonaqueous electrolytic solution secondary battery and polyfunctional monomer composition (B), the resin layer that makes it aggregate into sheet and obtain, can absorb in a large number and keep electrolytic solution, thereby finish the present invention.
Promptly the invention provides liquid-absorbent sheet, it is the liquid-absorbent sheet that comprises the liquid-absorbent resin layer, it is characterized in that: this liquid-absorbent resin layer is by to the monomer composition irradiation ultraviolet radiation that contains the monofunctional monomer composition (A) that comprises the monofunctional monomer (a) that can form the homopolymer of the non-aqueous solvent that is dissolved in nonaqueous electrolytic solution secondary battery and polyfunctional monomer composition (B) and polymerization obtains.
In addition, the invention provides a kind of non-aqueous electrolyte battery pack, be the non-aqueous electrolyte battery pack that is provided with battery with nonaqueous electrolyte unit, wired circuit board and is used to absorb the electrolytic solution absorption component of this electrolytic solution during from the leakage of battery with nonaqueous electrolyte unit generation electrolytic solution in battery case, it is characterized in that: this electrolytic solution absorption component is formed by aforesaid liquid-absorbent sheet.
The accompanying drawing summary
Figure 1A, Figure 1B and Fig. 1 C are respectively the sectional view of liquid-absorbent sheet of the present invention.
Fig. 2 is the skeleton view of non-aqueous electrolyte battery pack of the present invention.
Fig. 3 is the skeleton view of non-aqueous electrolyte battery pack of the present invention.
Fig. 4 is the explanatory view of the electrolytic solution absorption test in the simulated battery box.
Embodiment
At first, liquid-absorbent sheet of the present invention is described.
In the liquid-absorbent sheet of the present invention, shown in Figure 1A, be not limited only to the form that liquid-absorbent resin layer 1 forms sheet separately, form the form of liquid-absorbent resin layer 1 and be shown in the form that formed adhesion layer 3 on the face of liquid-absorbent resin layer 1 one sides etc. as Fig. 1 C but comprise as the single face of supporting mass that Figure 1B is shown in 2.Under the situation of the form of Fig. 1 C, liquid-absorbent sheet can be set in battery case easily.As adhesion layer 3, do not make particular restriction, can use known tackiness agent.In addition, do not use supporting mass, and be also contained in the liquid-absorbent sheet of the present invention in the form (form that does not have supporting mass 2 among Fig. 1 C) that the single face of liquid-absorbent resin layer is provided with adhesion layer.
As adhesion layer 3, do not make particular determination, use known tackiness agent to get final product, but as described later, in view of the liquid-absorbent resin layer according to composition, have to show fusible and do not show fusible situation, using when showing fusible liquid-absorbent resin layer as adhesion layer 3 uses, situation when using the on-liquid absorbent material as adhesion layer is compared, and can increase the liquid-absorbent amount of liquid-absorbent sheet.
As available supporting mass 2 in the liquid-absorbent sheet of the present invention, use electrolytic solution not see through the resin film that soaks into, for example the plastics film of polypropylene etc. etc. gets final product, and can absorb the non-woven fabrics that keeps plastic optical fibre non-aqueous solvent, that comprise polypropylene etc. etc. or paper etc. but also can use.When constituting supporting mass, can improve the absorption rate of non-aqueous solvent by this non-woven fabrics etc., thus preferred.
As the liquid-absorbent resin layer 1 that constitutes liquid-absorbent sheet of the present invention, use is to containing as the monofunctional monomer composition (A) of film-forming properties composition and as the monomer composition irradiation ultraviolet radiation of the polyfunctional monomer composition (B) of crosslinked composition and be polymerized to the polymeric membrane that sheet obtains, and wherein the monofunctional monomer composition (A) as the film-forming properties composition comprises the monofunctional monomer (a) that can form the homopolymer of the non-aqueous solvent that is dissolved in nonaqueous electrolytic solution secondary battery.
Among the present invention,, need to use the monofunctional monomer (a) that can form the homopolymer of the non-aqueous solvent that is dissolved in nonaqueous electrolytic solution secondary battery as monofunctional monomer composition (A).This is because the monofunctional monomer that only use to form the homopolymer that is not dissolved in such non-aqueous solvent during as monofunctional monomer composition (A), the inadequate cause of the liquid-absorbent of the resin layer that obtains.Here, so-called homopolymer is dissolved in non-aqueous solvent, be meant for non-aqueous solvent (at least a kind the mixed solvent that contains in methylcarbonate, propylene carbonate and the ethylene carbonate particularly described later, preferred equal-volume mixed solvent) 30 weight parts, homopolymer 1 weight part at the following dipping in the time of 24 hours of room temperature (about 23 ℃), has been reduced the situation of 10% quality at least.The minimizing of quality is to compare with the quality before the dipping by the dried quality that will flood the homopolymer that takes out the back from non-aqueous solvent to judge.When dissolving fully, quality reduces 100%.
This monofunctional monomer (a) is selected by its solubility parameter value (SP value (J/cm
3)
1/2), the value that deducts gained behind the solubility parameter value of non-aqueous solvent of the nonaqueous electrolytic solution secondary battery that should be suitable for for preferred in-1.0～8.0 scope, the more preferably material in 2.0～6.5 scope.Exceed this scope, this homopolymer becomes and is not dissolved in non-aqueous solvent in fact, and inadequate tendency appears in the liquid-absorbent of the resin layer that obtains.
In addition, solubility parameter value can be calculated (with reference to R.F.Fedors, Polym.Eng.Sci., 14 (2), p147, p472 (1947)) by the formula of following Fedors.About the solubility parameters of monofunctional monomer, be to calculate with regard to the repeating unit after the polymerization.In addition, in the formula of Fedors, " σ " is solubility parameters, and " V " is molecular volume (cm
3/ mol), " Ecoh " is bond energy (J/mol).
σ＝(∑Ecoh/V)
1/2
Here, as monofunctional monomer (a), use has used solubility parameter value, as SP (monomer) the mix value of its solubility parameters, to obtain by following formula during as the mixing monofunctional monomer (a) of SP monomer (a 2.) m mole 2. as 1. monomer (a 1.) n mole of SP, solubility parameter value.And the solubility parameters during with the monofunctional monomer more than 3 kinds can be calculated too.
SP (monomer) mix value=(SP 1. * n+SP 2. * m)/(n+m)
Object lesson as this monofunctional monomer (a), can enumerate imido acrylate (SP value=27.6), N-vinyl-2-Pyrrolidone (SP value=26.2), acryloyl morpholine (SP value=25), vinylformic acid benzyl ester (SP value=22.9), phenoxyethyl acrylate (SP value=22.6), N, N-diethyl acrylamide (SP value=20.6), polyalkylene glycol acrylate methoxyl group ester (oxyethane addition mole number (n)=9, SP value=19.6), polyalkylene glycol acrylate methoxyl group ester (oxyethane addition mole number (n)=3, SP value=20.1), vinylformic acid tetrahydro furfuryl ester (SP value=23), polyalkylene glycol acrylate phenoxy group ester (oxyethane addition mole number (n)=6, SP value=20.7) etc.Wherein, by the absorptivity viewpoint of electrolytic solution, preferred vinylformic acid benzyl ester, N-vinyl-2-Pyrrolidone, vinylformic acid tetrahydro furfuryl ester, acryloyl morpholine.Also can and with in them more than 2 kinds.In addition, by keeping, preferred also with vinylformic acid benzyl ester and acryloyl morpholine to the absorptivity of electrolytic solution and the equilibrated viewpoint of film hardness.Like this and the time spent, the proportioning of vinylformic acid benzyl ester and acryloyl morpholine (weight), the latter for a long time, the electrolytic solution absorptivity is good, but because the very hard easy breakage of film, so is preferably 30/70～70/30.
On the other hand, the solubility parameter value of non-aqueous solvent is preferably 17～28, and more preferably 18～23.Exceed this scope, when being used for lithium cell, the cycle characteristics of battery has the tendency of reduction.
As this non-aqueous solvent, can enumerate methylcarbonate (SP value=17.4), propylene carbonate (SP value=20.8), ethylene carbonate carbonates such as (SP value=22.5).They can use separately, and also two or more kinds may be used.Wherein especially preferred non-aqueous solvent can be enumerated the equal-volume mixed solvent (SP (solvent) mix value=20.2) of methylcarbonate, propylene carbonate and ethylene carbonate.The solubility parameters that mixes non-aqueous solvent also can be according to the solubility parameters and the usage quantity (mole number) of each non-aqueous solvent, according to and the method for calculation of solubility parameters when having used monofunctional monomer calculate.
In addition; the homopolymer of so-called monofunctional monomer (a); preferably in monofunctional monomer (a) 100 weight parts; mix ultraviolet polymerization initiator (for example 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, diacyl phosphine oxide, benzophenone or 2-methyl thioxanthone) 0.1～5 weight part, with 100～2000mJ/cm
2Energy density illumination wavelength 250～350nm ultraviolet ray and its polymerization is obtained.
In the present invention, monofunctional monomer composition (A) contains the monofunctional monomer (a) of above explanation, but very few, the liquid-absorbent amount of non-aqueous solvent has the tendency of minimizing, therefore preferably contains 20 moles of % at least.
In the monofunctional monomer composition (A), except that monofunctional monomer (a), in the scope of not damaging effect of the present invention, can also add other monofunctional monomers, for example hydroxyethyl acrylate (SP value=29.6), vinylformic acid (SP value=28.7), 2-ethylhexyl acrylate (SP value=18.9), vinylformic acid Lauryl Ester (SP value=18.7) etc.
In the present invention, polyfunctional monomer composition (B) is the composition that is used for importing to liquid-absorbent resin layer 1 crosslinking structure, the preferred monomer with 2 above acrylate residues that uses.For example, can use hydroxyl trimethylacetic acid neopentylglycol diacrylate, polyethyleneglycol diacrylate (oxyethane addition mole number (n)=14), bisphenol a diacrylate, phenyl glycidyl ether acrylate, phenyl glycidyl ether acrylate, hexamethylene diisocyanate carbamate prepolymer etc.
As the use level in the monomer composition of polyfunctional monomer composition (B), very few words, the shape-holding property of liquid-absorbent resin layer 1 is not enough, and too much words, can not fully absorb non-aqueous solvent, the therefore preferred cross-linking density that cooperates is 0.0001～0.17, more preferably in the amount of 0.001～0.1 scope.
Here, cross-linking density is meant the sense radix in the polyfunctional monomer in 1 molecule is made as a, and the mole number of the polyfunctional monomer in the monomer composition is made as b, when the mole number of the monofunctional monomer in the monomer composition is made as c, and the numerical value of trying to achieve according to following formula.
Cross-linking density=a * b/ (b+c)
Liquid-absorbent sheet of the present invention, as indicated above, be that the monomer composition that will contain monofunctional monomer composition (A) and polyfunctional monomer composition (B) is coated on the stripping film of polyethylene terephthalate thin film etc., by being carried out uviolizing, the coat film that obtains make it be polymerized to sheet, then peel by releasing sheet, obtain the material of form shown in Figure 1A, on non-woven fabrics, apply described monomer composition, make its polymerization or with the laminated words of material of form shown in non-woven fabrics and Figure 1A, obtain the material of the form of Fig. 1 (b), in addition, on the liquid-absorbent resin layer of the material of the form of Figure 1B, further apply and form or laminating adhesive, obtain the material of the form of Fig. 1 C.
As releasing sheet, when using the surface to apply concavo-convex embossing material processed, the liquid-absorbent resin layer surface becomes concaveconvex shape, and its surface-area increases.The result can the accelerating liquid absorbent sheet liquid-absorbent speed.
Can be not yet with on the attached stripping film that is coated to polyethylene terephthalate thin film etc. of the monomer composition that contains monofunctional monomer composition (A) and polyfunctional monomer composition (B), but directly be coated to the internal surface of the battery case 21 of Fig. 2, by uviolizing sheet materialization on this position.
Method as monomer composition being coated on releasing sheet or the non-woven fabrics etc. can adopt known in the past coating method, for example rolling method etc.In addition, as the example of polymerizable ultraviolet condition, can enumerate usually under 15～25 ℃, with 100～2000J/cm
2The ultraviolet condition of energy density irradiation 250～350nm wavelength.
In addition, when the liquid-absorbent resin layer itself possesses binding property, use (as the monofunctional monomer of composition (A), use vinylformic acid tetrahydro furfuryl ester (SP value=23), vinylformic acid benzyl ester (SP value=22.9), vinylformic acid benzene oxygen ethyl ester (SP value=22.6), polyalkylene glycol acrylate phenoxy group ester (oxyethane addition mole number (n)=6, SP value=20.7), or polyalkylene glycol acrylate methoxyl group ester (oxyethane addition mole number (n)=3, SP value=20.1) time, liquid-absorbent resin layer itself shows binding property, therefore bonding coat can be set, and according to the form of Figure 1A or Figure 1B, directly attach on the cell box, and can not utilize lamination methods, at room temperature utilize hand roller that the liquid-absorbent resin layer is attached on the supporting mass.(with reference to Figure 1B).In addition, as the planeform of liquid-absorbent sheet, in view of the leakage of cylinder battery is by anodal leakage mostly, for attach to positive terminal around, preferably make toroidal.
Among the present invention, preferably in the liquid-absorbent resin layer 1 of liquid-absorbent sheet of the present invention, further add fire retardant (aqueous phosphoric acid ester flame retardant, aluminium hydroxide, melamine cyanurate etc.).Can give liquid-absorbent sheet thus with flame retardant resistance.When particularly using aqueous phosphoric acid ester fire retardant, liquid-absorbent resin layer 1 be can give, V-0, the V-1 of UL-94 standard or the flame retardant resistance of V-2 level specifically can be given with flame retardant resistance as fire retardant.And, the phosphoric acid ester flame retardant, under atmospheric pressure, usually in the scope below 250 ℃ more than-13 ℃, preferably be aqueous in room temperature range, so can give the binding property of liquid-absorbent resin layer 1 with excellence.If liquid-absorbent resin layer 1 shows binding property, just can directly liquid-absorbent resin layer 1 be attached on the nonaqueous electrolytic solution secondary battery box, therefore there is no need to be provided with specially adhesion layer, do not make thickness that the thickness of liquid-absorbent resin layer 1 is thinner than adhesion layer also can, thereby can make the liquid-absorbent amount of this liquid-absorbent sheet not reduce.And then, when using aqueous phosphoric acid ester flame retardant as fire retardant, unexpectedly be, even handle (for example in the processing that keeps 96 hours under the environment of 40 ℃ of temperature, humidity 90%RH) at the hydrothermal aging of liquid-absorbent sheet after, still can make the insulating resistance value of the liquid-absorbent resin layer 1 after handling be preferably and be not less than 1 * 10
12Ω.
As the aqueous phosphoric acid ester flame retardant of available among the present invention, can enumerate two (phenylbenzene) esters of phosphoric acid dihydroxyphenyl propane, two (phenylbenzene) esters of quinol phosphate, phosphoric acid phenyl two (xylyl) ester, lindol, tricresyl phosphate base diphenyl, tricresyl phosphate (xylyl) ester, di(2-ethylhexyl)phosphate tolyl diphenyl, two (phenylbenzene) esters of phosphoric acid Resorcinol, phosphoric acid 2-ethylhexyl diphenyl etc.Wherein, set out, can preferably use two (phenylbenzene) esters of phosphoric acid dihydroxyphenyl propane, two (phenylbenzene) esters of quinol phosphate or phosphoric acid phenyl two (xylyl) ester by giving fusible viewpoint.
The words that the usage quantity of aqueous phosphoric acid ester flame retardant is very few, can not obtain sufficient flame retardant resistance, and too much words also can not get sufficient flame retardant resistance, therefore, summation 100 weight parts with respect to monofunctional monomer composition (A) and polyfunctional monomer composition (B), be preferably 70～200 weight parts, more preferably 100～150 weight parts.
Liquid-absorbent sheet of the present invention, the non-aqueous electrolyte battery pack that is provided with battery with nonaqueous electrolyte unit, wired circuit board and is used for absorbing the electrolytic solution absorption component of this electrolytic solution in battery case by the leakage of battery with nonaqueous electrolyte unit generation electrolytic solution the time can preferably use as this electrolytic solution absorption component.For example, as shown in Figure 2, be provided with in the cell box of battery with nonaqueous electrolyte unit 23 on the wired circuit board 22 that in battery case 21, is provided with, electrolytic solution absorption component as be used to absorb this electrolytic solution when by battery with nonaqueous electrolyte unit 23 the electrolytic solution leakage taking place can dispose the liquid-absorbent sheet 26 illustrated as Figure 1A between wired circuit board 22 and battery with nonaqueous electrolyte unit 23.Here, battery with nonaqueous electrolyte unit 23 is connected by plain conductor 24 with wired circuit board 22, further is communicated with outside terminal 25.In addition, as shown in Figure 3, also the liquid-absorbent sheet 27 that illustrates among Fig. 1 C can be configured to become the mode of battery with nonaqueous electrolyte unit 23 1 sides at battery with nonaqueous electrolyte unit 23 upper support bodies.
In addition, in Fig. 2 and Fig. 3, the shape of the battery case in the non-aqueous electrolyte battery pack is made as rectangular parallelepiped, the shape of battery unit is made as round shape, but in non-aqueous electrolyte battery pack of the present invention, can be not limited to above shape, and be set to meet shape, the configuration formation of application target.In addition, the kind of battery unit does not limit yet.
Above Shuo Ming non-aqueous electrolyte battery pack of the present invention, as nonaqueous electrolytic solution absorption component material, use is by containing monofunctional monomer composition (A), form with the monomer composition of polyfunctional monomer composition (B), and the liquid-absorbent resin that possesses excellent liquid absorbent resin layer aspect the absorption retentivity of nonaqueous electrolytic solution, wherein this monofunctional monomer composition (A) comprises the monofunctional monomer (a) that can form the homopolymer of the non-aqueous solvent that is dissolved in nonaqueous electrolytic solution secondary battery, even therefore when producing the nonaqueous electrolytic solution leakage, also can greatly suppress the corrosion of wired circuit or the generation of short circuit by battery unit.
Embodiment
Following according to embodiment, the present invention is specifically described.
Reference example
Described in hereinafter explanation, the homopolymer that is made of monofunctional monomer is investigated with respect to the solubleness of the non-aqueous solvent of nonaqueous electrolytic solution secondary battery.
That is, in simple function monomer 100 mass parts, add Photoepolymerizationinitiater initiater (2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; D1173, Ciba Specialty Chemicals company) 1 weight part, utilize roller coating machine that the mixture that obtains is coated on the polyethylene terephthalate thin film, with 2000mJ/em
2The ultraviolet ray of energy density irradiation 365nm wavelength, make its polymerization.With polymeric membrane (homopolymer film) 1 mass parts that obtains, after flooding 24 hours in equal-volume mixture (SP (solvent) mix value=20.2) 300 mass parts under 23 ℃, in methylcarbonate/propylene carbonate/ethylene carbonate, filtering mixt, solid substance residual on the strainer was descended dry 1 hour at 100 ℃, calculate solubleness (wt%) according to following calculating formula.The result who obtains is as shown in table 1.W in the formula
1Be the quality of the polymeric membrane before flooding, W
2Admittedly form the quality of branch for drying.
Solubleness=((W
1-W
2)/W
1) * 100
Table 1
| Monofunctional monomer | The SP value | SP value difference with solvent | Solubleness wt% |
| Hydroxyethyl acrylate | 29.6 | 9.4 | 3 |
| Vinylformic acid | 28.7 | 8.5 | 5 |
| The imido acrylate | 27.6 | 7.4 | 100 |
| N-vinyl-2-Pyrrolidone | 26.2 | 6.0 | 100 |
| | 25 | 4.8 | 100 |
| The vinylformic acid benzyl ester | 22.9 | 2.7 | 100 |
| Vinylformic acid benzene oxygen ethyl ester | 22.6 | 2.4 | 85 |
| N, N-diethyl acrylamide | 20.6 | 0.4 | 100 |
| Polyalkylene glycol acrylate methoxyl group ester (n=9) | 19.6 | -0.6 | 100 |
| Polyalkylene glycol acrylate methoxyl group ester (n=3) | 20.1 | -0.1 | 100 |
| Polyalkylene glycol acrylate phenoxy group ester (n=6) | 20.7 | 0.5 | 100 |
| The vinylformic acid tetrahydro furfuryl ester | 23.0 | 2.8 | 100 |
| 2-ethylhexyl acrylate | 18.9 | 1.3 | 3 |
According to table 2 and the described combined amount of table 3, with table 2 and the described simple function monomer of table 3 and as the hydroxyl trimethylacetic acid neopentylglycol diacrylate of polyfunctional monomer, mix as 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone of polymerization starter, utilize rolling method to be coated on the polyethylene terephthalate thin film, at 2000mJ/cm
2Energy density under the ultraviolet ray of irradiation 365nm wavelength make its polymerization, polymeric membrane by peeling off on the polyethylene terephthalate thin film, is obtained the liquid-absorbent sheet of individual layer.
Under 23 ℃, the liquid-absorbent sheet that obtains is immersed in the equal-volume mixed solvent (SP (solvent) mix value=20.2) of the methylcarbonate/propylene carbonate/ethylene carbonate of large volume, after 2 hours the shape of visual observations liquid-absorbent resin layer the time, from mixed solvent, take out, wipe the mixed solvent on surface immediately, gravimetry is obtained expansion multiplying power.The result who obtains is as shown in table 2.And the SP value of monofunctional monomer (SP (monomer) value), the shape with the cross-linking density of the liquid-absorbent resin layer of the SP value difference (Δ SP value) of solvent, liquid-absorbent sheet, after flooding are like shown in table 2 and the table 3.
Table 2
| Composition | Embodiment (weight part) | |||||
| 1 | 2 | 3 | 4 | 5 | 6 | |
| The vinylformic acid benzyl ester | 100 | 100 | 100 | - | 30 | 100 |
| N-vinyl-2-Pyrrolidone | - | - | - | 100 | - | - |
| Vinylformic acid | - | - | - | - | 70 | - |
| | 1 | 0.1 | 10 | 1 | 1 | 20 |
| | 1 | 1 | 1 | 1 | 1 | 1 |
| SP (monomer) value | 22.9 | 22.9 | 22.9 | 26.2 | 27.8 | 22.9 |
| Δ SP value | 2.7 | 2.7 | 2.7 | 6.0 | 7.6 | 2.7 |
| Cross-linking density | 0.010 | 0.001 | 0.091 | 0.007 | 0.005 | 0.167 |
| Expansion multiplying power (doubly) | 10 | 10 | 3 | 10 | 3 | 1.6 |
| Dipping back shape | Film | Gel | Film | Film | Film | Film |
Table 3
| Comparative example (weight part) | |||
| 1 | 2 | 3 | |
| The vinylformic acid benzyl ester | 100 | - | - |
| Vinylformic acid | - | 100 | - |
| 2-ethylhexyl acrylate | - | - | 100 |
| Multi-functional monomer | - | 1 | 1 |
| | 1 | 1 | 1 |
| SP (monomer) value | 22.9 | 28.7 | 18.9 |
| Δ SP value | 2.7 | 8.5 | -1.3 |
| Cross-linking density | 0.000 | 0.005 | 0.005 |
| Expansion multiplying power (doubly) | Dissolving | 1.1 | 1.1 |
| Dipping back shape | Aqueous | Film | Film |
By the result of table 2 and table 3 as can be known, the liquid-absorbent sheet of embodiment 1, expansion multiplying power is 10 times, and after absorbing the non-aqueous solvent expansion, still keep film shape, when producing electrolysis the liquid leakage, be useful as the electrolytic solution absorption component that is used to absorb this electrolytic solution by the battery with nonaqueous electrolyte unit.
In addition, the liquid-absorbent sheet of embodiment 2～6, not only embody when using no problem performance aspect practical as the electrolytic solution absorption component, and as can be known by the result of embodiment 2, when cross-linking density reduced, absorbing shape after non-aqueous solvent expands had by film shape and becomes gelatinous tendency.Otherwise by the result of embodiment 3 and embodiment 6 as can be known, when cross-linking density increased, expansion multiplying power had the tendency of reduction.By the result of embodiment 4 as can be known, even use N-vinyl-2-Pyrrolidone to replace the vinylformic acid benzyl ester, also can obtain good result as monofunctional monomer.By the result of embodiment 5 as can be known, and during with the monofunctional monomer of the homopolymer that is insoluble to non-aqueous solvent, expansion multiplying power has the tendency of reduction.
On the other hand, by the result of comparative example 1 as can be known, do not use fully under the situation of polyfunctional monomer, the liquid-absorbent resin layer is dissolved in non-aqueous solvent, can not use as the electrolytic solution absorption component.By the result of comparative example 2 as can be known, excessive when the SP of monofunctional monomer value, when its homopolymer was not dissolved in non-aqueous solvent in fact, expansion multiplying power was too small, can not use as the electrolytic solution absorption component.Otherwise by the result of comparative example 3 as can be known, the SP value of monofunctional monomer is too small, even its homopolymer is not dissolved in fact under the situation of non-aqueous solvent, expansion multiplying power is too small, can not use as the electrolytic solution absorption component.
Embodiment 7 (the electrolytic solution absorption test in the simulated battery box)
As shown in Figure 4, prepare the case 41 of the ABS resin of long 7.0cm * wide 7.9cm * high 2.3cm, use the liquid-absorbent sheet 42 of the embodiment 1 that commercially available tackiness agent will long 6.5cm * wide 6.5cm * thick 100 μ m to attach to the bottom of case, pack into thereon 3 the joint lithium ion batteries 43, glass epoxide base material 44 is set as circuit substrate in part with the battery adjacency.
Then, use electric drill to open a hole h at the lateral parts of the battery of the center of 3 batteries 43, the electrolytic solution that carries out spilling from here absorbs the test in the liquid-absorbent sheet.Open a hole h, after the placement 1 round the clock, observe in the cell box, find on the glass epoxide base material, to can't see wetting.In addition, the weight reduction that has the battery of hole h is 2.5g, and the weight increasing amount of liquid-absorbent sheet is 2.5g, and all electrolytic solution that hence one can see that spills have all been absorbed by liquid-absorbent sheet.
Embodiment 8～15
According to the described use level of table 4, with the described simple function monomer of table 4, as multi-functional monomeric polyethyleneglycol diacrylate (oxyethane addition mole number=14; 14EG-A, common prosperity society chemistry), mix as the 2-hydroxy-2-methyl-1-phenyl-propane of polymerization starter-1-ketone, utilize rolling method to be coated on the polyethylene terephthalate thin film, at 2000mJ/cm
2Energy density under the ultraviolet ray of irradiation 365nm wavelength make its polymerization, polymeric membrane by peeling off on the polyethylene terephthalate thin film, is obtained the liquid-absorbent sheet (210g/m of individual layer
2).
In the equal-volume mixed solvent (SP (solvent) mix value=20.2) of methylcarbonate/propylene carbonate/ethylene carbonate, dissolving phosphorus hexafluoride acid lithium is as ionogen, make it become 1mol/l, be prepared into electrolytic solution thus, this electrolytic solution 0.2ml is added drop-wise on the good liquid-absorbent sheet 0.03g of prepared beforehand, measures visual following its time that is absorbed fully.In addition, flood in the electrolytic solution under 23 ℃, in abundant amount, the shape of visual observations liquid-absorbent resin layer the time, take out from mixed solvent after 3 hours, wipe the mixed solvent on surface immediately, gravimetry is obtained expansion multiplying power.In addition, use damp and hot stove (40 ℃, 90%RH, 96 hours) heating liquid absorbent sheet after, carry out the test of turgidity.The result who obtains is as shown in table 5.
In addition, utilize hand roller method (23 ℃) or lamination methods (80 ℃) on the two sides of the liquid-absorbent sheet of prepared beforehand, to attach the wide polypropylene non-woven fabric of 5cm (ュ ニ チ カ company), use tensile testing machine (テ Application シ ロ Application, オ リ エ Application テ Star Network company), under the T separation mode, measure bond strength.In addition, utilize hand roller method (23 ℃) or lamination methods (80 ℃) liquid-absorbent sheet that the 3cm of prepared beforehand is wide to attach to the Ni face, utilize tensile testing machine (テ Application シ ロ Application, オ リ エ Application テ Star Network company) under the T separation mode, to measure bond strength.The result who obtains is as shown in table 5.
In addition, the SP value of monofunctional monomer (SP (monomer) value), the shape with the cross-linking density of the liquid-absorbent resin layer of the SP value difference (Δ SP value) of solvent, liquid-absorbent sheet, after flooding etc. are as shown in table 5.
Table 4
| Composition | Embodiment (weight part) | |||||||
| 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | |
| The vinylformic acid tetrahydro furfuryl ester | 100 | - | - | - | - | - | - | - |
| The vinylformic acid benzyl ester | - | 100 | - | - | - | - | - | - |
| Vinylformic acid benzene oxygen ethyl ester | - | - | 100 | - | - | - | - | - |
| Polyalkylene glycol acrylate phenoxy group ester (n=6) | - | - | - | 100 | - | - | - | - |
| Polyalkylene glycol acrylate methoxyl group ester (n=3) | - | - | - | - | 100 | - | - | - |
| Polyalkylene glycol acrylate methoxyl group ester (n=9) | - | - | - | - | - | 100 | - | - |
| Acryloyl morpholine | - | - | - | - | - | - | 100 | - |
| N, N-diethyl acrylamide | - | - | - | - | - | - | - | 100 |
| Multi-functional monomer | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Photoepolymerizationinitiater initiater | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
Table 5
| Composition | Embodiment | |||||||
| 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | |
| (turgidity) no wet heat treatment | ||||||||
| Quantitatively drip (minute) | 30 | 100 | 120 | 40 | 15 | 15 | 120＜ | 180 |
| During dipping (doubly) | 9.0 | 9.4 | 9.6 | 8.2 | 8.6 | 9.0 | 2.3 | 18 |
| (turgidity) has wet heat treatment | ||||||||
| Quantitatively drip (minute) | 30 | 130 | 160 | 60 | 20 | 25 | 120＜ | 200 |
| During dipping (doubly) | 9.0 | 9.2 | 9.0 | 8.1 | 8.5 | 8.5 | 2.0 | 17 |
| Bond strength for non-woven fabrics | ||||||||
| Hand roller (kg/5cm) | 0.4 | 0.03 | 0.03 | 0.1 | 0.03 | 0 | 0 | 0 |
| Heat lamination (kg/5cm) | 0.7 | 0.03 | 0.03 | 0.1 | 0.03 | 0 | 0 | 0.3 |
| Bond strength to the Ni face | ||||||||
| Hand roller (kg/3cm) | 0.3 | 0.02 | 0.02 | 0.08 | 0.03 | 0 | 0 | 0 |
| SP (monomer) | 23 | 22.9 | 22.6 | 20.7 | 20.1 | 19.6 | 25 | 20.6 |
| Δ SP value | 2.8 | 2.7 | 2.4 | 0.5 | -0.1 | -0.6 | 4.8 | 0.4 |
| Cross-linking density | 0.002 | 0.002 | 0.003 | 0.004 | 0.003 | 0.006 | 0.002 | 0.002 |
| Dipping back shape | Film | Film | Film | Film | Film | Film | Film | Film |
As shown in Table 5, the liquid-absorbent sheet of embodiment 8～13, although the liquid-absorbent speed existence of electrolytic solution is poor when quantitatively dripping, but the expansion multiplying power during dipping is about 8～9 times, and absorb and still can keep film shape after non-aqueous solvent expands, when producing electrolysis the liquid leakage, be useful as the electrolytic solution absorption component that is used to absorb this electrolytic solution by the battery with nonaqueous electrolyte unit.
In addition, the liquid-absorbent sheet of embodiment 14 is compared with the liquid-absorbent sheet of embodiment 8～13, though expansion multiplying power is little, demonstrates performance without a doubt aspect practical when using as the electrolytic solution absorption component.In addition, the liquid-absorbent sheet of embodiment 15 is compared with the liquid-absorbent sheet of embodiment 8～13, though the absorption rate of electrolytic solution is slow when quantitatively dripping, demonstrates excellent expansion multiplying power.
In addition, the liquid-absorbent sheet of embodiment 8～12 because its liquid-absorbent resin layer itself shows binding property, therefore can not be provided with adhesion layer in addition.Particularly the liquid-absorbent resin layer of the liquid-absorbent sheet of embodiment 8 demonstrates excellent adhesion characteristic.
Embodiment 16 (experiment a～e), comparative example 4 (experiment f～h) and comparative example 5
According to table 1 or the described use level of table 2, with the simple function monomer described in table 6 and the table 7, as the urethane acrylate (AH600, common prosperity society) of polyfunctional monomer, mix as the 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone (D1173, Ciba Specialty Chemicals) of polymerization starter and aqueous phosphoric acid ester flame retardant or solid ammonium polyphosphate flame retardant, utilize rolling method to be coated on the polyethylene terephthalate thin film, at 2000mJ/cm
2Energy density under the ultraviolet ray of irradiation 365nm wavelength make its polymerization, press flame retardant nonwoven fabric (Japanese Villene company) under the room temperature on the polymeric membrane upper strata, by peeling off on the polyethylene terephthalate thin film, obtain thus 2 layers of structure liquid-absorbent sheet.
For the liquid-absorbent sheet that obtains,, experimentize for expansion multiplying power, the insulativity of flame retardant resistance, binding property, electrolytic solution according to following explanation.
(flame retardant resistance)
According to the UL-94 standard, the liquid-absorbent sheet that obtains is tested, estimate its flame retardant resistance.The result who obtains is shown in table 6 and table 7.If V-0, V-1 or V-2 level, demonstrate flame retardant resistance without a doubt aspect practical.
(binding property)
Utilize hand roller method (23 ℃) to attach the wide polypropylene non-woven fabric of 5cm (Japanese Villene company) exposing on the liquid-absorbent resin layer of liquid-absorbent sheet, use tensile testing machine (テ Application シ ロ Application, オ リ エ Application テ Star Network company) under the T separation mode, to measure bond strength.The result who obtains is shown in table 6 and table 7.
(expansion multiplying power)
In the equal-volume mixed solvent of methylcarbonate/propylene carbonate/ethylene carbonate, dissolving phosphorus hexafluoride acid lithium is as ionogen, make it become 1mol/l, be prepared into electrolytic solution thus, under 23 ℃, liquid-absorbent sheet is immersed in this electrolytic solution, by taking out in the electrolytic solution, wipe the mixed solvent on surface immediately after 3 hours, gravimetry is obtained expansion multiplying power.The result who obtains is shown in table 6 and table 7.
(insulativity)
Insulating resistance value (Ω) before and after the wet heat treatment of the liquid-absorbent resin layer of the liquid-absorbent sheet that mensuration obtains.The result who obtains is shown in table 6 and table 7.
Table 6
| Composition | Embodiment 16 (weight part) | ||||
| Experiment a | Experiment b | Experiment c | Experiment d | Experiment e | |
| The vinylformic acid benzyl ester | 70 | 70 | 70 | 70 | 70 |
| Acryloyl morpholine | 30 | 30 | 30 | 30 | 30 |
| Polyfunctional monomer | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Photoepolymerizationinitiater initiater | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Two (phenylbenzene) esters of phosphoric acid dihydroxyphenyl propane | 70 | 100 | 150 | 200 | - |
| Two (phenylbenzene) esters of quinol phosphate | - | - | - | - | 100 |
| Flame retardant resistance (UL-94) | V-0 | V-0 | V-0 | V-2 | V-2 |
| Binding property (kgf/5cm) | 0.4 | 0.6 | 0.5 | 0.5 | 0.7 |
| Expansion multiplying power (doubly) | 9 | 8 | 6 | 6 | 7 |
| Insulativity (Ω) (before the wet heat treatment) | 4×10 12 | 4×10 12 | 3×10 12 | 3×10 12 | 1×10 10 |
| Insulativity (Ω) (after the wet heat treatment) | 1×10 12 | 1×10 12 | 1×10 12 | 1×10 12 | 1×10 9 |
Table 7
| Composition | Comparative example 4 (weight part) | Comparative example 5 (weight part) | ||
| Experiment f | Experiment g | Experiment h | ||
| The vinylformic acid benzyl ester | 70 | 70 | 70 | 70 |
| Acryloyl morpholine | 30 | 30 | 30 | 30 |
| Polyfunctional monomer | 0.5 | 0.5 | 0.5 | 0.5 |
| Photoepolymerizationinitiater initiater | 0.5 | 0.5 | 0.5 | 0.5 |
| Two (phenylbenzene) esters of phosphoric acid dihydroxyphenyl propane | 0 | 50 | 250 | - |
| Ammonium polyphosphate | - | - | - | 200 |
| Flame retardant resistance (UL-94) | Do not have | Do not have | Do not have | V-0 |
| Binding property (kgf/5cm) | Do not have | Do not have | 0.3 | Do not have |
| Expansion multiplying power (doubly) | 9 | 9 | 4 | - |
| Insulativity (Ω) (before the wet heat treatment) | 9×10 13 | 9×10 13 | 9×10 13 | 3×10 14 |
| Insulativity (Ω) (after the wet heat treatment) | 2×10 12 | 2×10 12 | 2×10 12 | 3×10 10 |
As shown in Table 6, the liquid-absorbent sheet of experiment a～d of embodiment 16 demonstrates excellent flame-retardant performance and binding property, and expansion multiplying power is more than 6 times, and the insulation characterisitic excellence.In addition, the liquid-absorbent sheet of experiment e, at flame retardant resistance, binding property and expansion multiplying power each side liquid-absorbent sheet material, more excellent aspect binding property no less than experiment a～d.But, low some grades aspect insulativity.But the variation before and after the wet heat treatment is little, excellence aspect storage stability.
In addition, as shown in Table 7, the liquid-absorbent sheet of the experiment f～h of comparative example 4, not only do not adding under the two situations of (phenylbenzene) ester of phosphoric acid dihydroxyphenyl propane as aqueous phosphoric acid ester flame retardant, and when its addition is very few and too much, the tendency of the flame retardant resistance that can not obtain wishing appears also.In addition, use in the comparative example 5 of solid ammonium polyphosphate flame retardant, originally do not have binding property, and after the wet heat treatment, insulativity greatly reduces.
Embodiment 17 (the electrolytic solution absorption test in the simulated battery box)
As shown in Figure 4, prepare the case 41 of the ABS resin of long 7.0cm * wide 7.9cm * high 2.3cm, use the liquid-absorbent sheet 42 of the embodiment 1 that commercially available tackiness agent will long 6.5cm * wide 6.5cm * thick 100 μ m to attach to the bottom of case, pack into thereon 3 the joint lithium ion batteries 43, glass epoxide base material 44 is set as circuit substrate in part with the battery adjacency.
Then, use electric drill to open a hole h at the lateral parts of the battery of the center of 3 batteries 43, the electrolytic solution that carries out spilling from here absorbs the test in the liquid-absorbent sheet.Open a hole h, after the placement 1 round the clock, observe in the cell box, find on glass epoxide base material 44, to can't see wetting.In addition, the weight reduction that has the battery of hole h is 2.5g, and the weight increasing amount of liquid-absorbent sheet is 2.5g, and all electrolytic solution that hence one can see that spills have all been absorbed by liquid-absorbent sheet.
Industrial applicibility
Liquid-absorbent sheet of the present invention has the liquid-absorbent resin bed that the nonaqueous electrolytic solution of nonaqueous electrolytic solution secondary battery is shown excellent liquid-absorbent. Therefore, the electrolyte absorption component as nonaqueous electrolytic solution box (especially lithium ion nonaqueous electrolytic solution secondary battery box) is useful.
In addition, when in the liquid-absorbent resin bed of liquid-absorbent sheet of the present invention, using aqueous phosphate flame retardant, the liquid-absorbent resin bed demonstrates excellent liquid-absorbent and cohesive for the nonaqueous electrolytic solution of the nonaqueous electrolytic solution secondary battery that consists of nonaqueous electrolytic solution box (especially lithium ion nonaqueous electrolytic solution secondary battery box), and then demonstrates excellent anti-flammability. Therefore, liquid-absorbent sheet of the present invention is useful as the electrolyte absorption component of nonaqueous electrolytic solution box.
Claims (12)
1. nonaqueous electrolytic solution absorbent sheet, it is the nonaqueous electrolytic solution absorbent sheet that comprises the absorbency resin layer, it is characterized in that:
This absorbency resin layer is by to comprising the monomer composition irradiation ultraviolet radiation of monofunctional monomer composition (A) with vinyl or acryl and the polyfunctional monomer composition (B) with 2 above acryls; its polymerization is obtained; wherein with respect to 100 weight part monofunctional monomer compositions (A); polyfunctional monomer composition (B) is below 20 weight parts; described monofunctional monomer composition (A) contains the monofunctional monomer (a) that can form the homopolymer in the non-aqueous solvent that is dissolved in nonaqueous electrolytic solution secondary battery; and in the monofunctional monomer composition (A); the content that can form the monofunctional monomer (a) of the homopolymer in the non-aqueous solvent that is dissolved in nonaqueous electrolytic solution secondary battery is at least 30% weight; described monofunctional monomer (a) is the vinylformic acid benzyl ester; N-vinyl-2-Pyrrolidone; the imido acrylate; acryloyl morpholine; vinylformic acid benzene oxygen ethyl ester; N, N-diethyl acrylamide; polyalkylene glycol acrylate methoxyl group ester; vinylformic acid tetrahydro furfuryl ester or polyalkylene glycol acrylate phenoxy group ester.
2. nonaqueous electrolytic solution absorbent sheet as claimed in claim 1 wherein, from the solubility parameter value of described monofunctional monomer (a), deducts the value of gained behind the solubility parameter value of this non-aqueous solvent, in-1.0～8.0 scope.
3. nonaqueous electrolytic solution absorbent sheet as claimed in claim 2, the solubility parameter value of wherein said non-aqueous solvent is in 17～28 scope.
4. nonaqueous electrolytic solution absorbent sheet as claimed in claim 1, wherein said non-aqueous solvent comprises at least a kind in methylcarbonate, propylene carbonate and the ethylene carbonate, this homopolymer is to mix ultraviolet polymerization initiator 0.1～5 weight part in this monofunctional monomer (a) 100 weight parts, and polymerization obtains by uviolizing.
5. nonaqueous electrolytic solution absorbent sheet as claimed in claim 4, wherein said homopolymer are to be dissolved in the material of this mixed solvent with respect to its 1 weight part of dipping under the non-aqueous solvent 30 weight part room temperatures in the time of 24 hours.
6. nonaqueous electrolytic solution absorbent sheet as claimed in claim 1, wherein, the cross-linking density of absorbency resin layer is 0.0001～0.17.
7. as each described nonaqueous electrolytic solution absorbent sheet of claim 1～5, wherein said absorbency resin layer is formed on the supporting mass.
8. nonaqueous electrolytic solution absorbent sheet as claimed in claim 7, wherein said supporting mass can absorb and keep nonaqueous electrolytic solution.
9. nonaqueous electrolytic solution absorbent sheet as claimed in claim 1, wherein said monomer composition further contain aqueous phosphoric acid ester flame retardant.
10. nonaqueous electrolytic solution absorbent sheet as claimed in claim 9, wherein said aqueous phosphoric acid ester flame retardant are two (phenylbenzene) esters of phosphoric acid dihydroxyphenyl propane, two (phenylbenzene) esters of quinol phosphate, phosphoric acid phenyl two (xylyl) ester, lindol, tricresyl phosphate base diphenyl, tricresyl phosphate (xylyl) ester, di(2-ethylhexyl)phosphate tolyl diphenyl, two (phenylbenzene) esters of phosphoric acid Resorcinol or phosphoric acid 2-ethylhexyl diphenyl.
11. as claim 9 or 10 described nonaqueous electrolytic solution absorbent sheets, wherein said monomer composition, with respect to summation 100 weight parts of monofunctional monomer composition (A) and polyfunctional monomer composition (B), contain aqueous phosphoric acid ester flame retardant with the ratio of 70～200 weight parts.
12. non-aqueous electrolyte battery pack, be the non-aqueous electrolyte battery pack that is provided with battery with nonaqueous electrolyte unit, wired circuit board and is used to absorb the electrolytic solution absorption component of this electrolytic solution during from the leakage of battery with nonaqueous electrolyte unit generation electrolytic solution in battery case, it is characterized in that: this electrolytic solution absorption component is formed by each described nonaqueous electrolytic solution absorbent sheet of claim 1～11.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP039776/2003 | 2003-02-18 | ||
| JP2003039776 | 2003-02-18 | ||
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| JP289270/2003 | 2003-08-07 |
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| CN108886121A (en) * | 2016-04-01 | 2018-11-23 | 株式会社Lg化学 | battery module |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2002005817A1 (en) * | 2000-07-18 | 2002-01-24 | William Lowenstein | Pharmaceutical composition based on cocaethylene and use thereof for treating psychoactive substance dependence |
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| WO2002005817A1 (en) * | 2000-07-18 | 2002-01-24 | William Lowenstein | Pharmaceutical composition based on cocaethylene and use thereof for treating psychoactive substance dependence |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108886121A (en) * | 2016-04-01 | 2018-11-23 | 株式会社Lg化学 | battery module |
| CN108886121B (en) * | 2016-04-01 | 2021-11-30 | 株式会社Lg化学 | Battery module |
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